This invention relates to imaging elements and in particular to imaging elements which involve the transfer of colorant from a substrate.
There is a continuing need for imaging materials that are dry-processed, i.e., which do not need aqueous or other chemical treatments in order to develop or fix the image. There is a particular need in the area of colour reproduction, e.g., colour proofing, where the demands in terms of resolution are extremely high. Peel-apart and thermal transfer are attractive technologies for this purpose, but poor resolution has hitherto been a problem.
Peel-apart imaging is well-known in the art, and is described, for example, in xe2x80x9cImaging Systemsxe2x80x9d (Jacobson and Jacobson, Focal Press, 1976, p.213), and in patent literature. Suitable materials generally comprise a photosensitive colorant layer sandwiched between a substrate and a stripping sheet or layer. Light exposure through a suitable mask, followed by careful removal of the stripping sheet, causes an imagewise partitioning of the colorant layer between the substrate and stripping sheet. Both positive- and negative-acting systems are known, i.e., the colorant may be selectively removed from or retained by the substrate in exposed areas.
Because the resulting image consists solely of areas of maximum density and areas of zero density, such systems are ideally suited to half tone reproduction. Full colour images may be provided by generating separate (y,m,c,k) images on transparent substrates and assembling them in register (overlay), as described, for example in U.S. Pat. No. 4,282,308, U.S. Pat. No. 4,286,043 and EP385466, and exemplified by the Du Pont xe2x80x9cCromacheckxe2x80x9d system. There is increasing interest in applying peel-apart technology to the formation of integral proofs, in which successive y,m,c,k images are assembled on a common substrate, as described in U.S. Pat. No. 4,489,153 and EP 385466, and British Patent Application No. 92 25687.4
Typically, the colorant layers described in the prior art comprise one or more pigments dispersed in a photocurable medium comprising suitable monomer(s), photoinitiator(s) and binder(s). Other layers may be present, such as adhesive layers, release layers, etc, but the prime cause of the image differential is photopolymerisation.
It is known to add surfactants, including fluorinated surfactants, to the photocurable colorant layers described above. Fluorinated surfactants are frequently used as coating aids in the imaging industry generally, e.g., to promote even wetting of substrates, enhance coating uniformity and prevent striations, as described, for example, in U.S. Pat. No. 4,504,567, EP 230995, EP 239082, JP 61-292137 and JP 62-036657, and peel-apart imaging elements are no exception. Generally, the quantities of surfactant involved are small. For example, EP385466 (table 2, p.16) shows the use of fluorosurfactant in peel-apart colorant layers to the extent of 0.068 wt % of the total solids. Of the formulations disclosed, the cyan layer has the lowest pigment content, and this still represents a pigment: surfactant ratio of about 70:1. Likewise EP373532 discloses the use of fluorosurfactants in the photocurable colorant layers of peel-apart imaging elements, but does not give details of preferred quantities and does not mention any effects on the speed or resolution of the media. The Examples disclose pigment:surfactant ratios ranging from 57.8:1 to 20.9:1.
Thermal transfer imaging is also well known in the art. Two types of donor media may be distinguished, namely sublimation (or diffusion) transfer media, and mass transfer media. In the former, dyes are caused to migrate from a donor to a receptor in amounts proportional to the energy applied, giving continuous tone images, while in the latter, zero or 100% transfer of the colorant layer takes place according to whether the applied energy exceeds a given level. The latter type is highly suited to half tone reproduction since the resulting images consist of areas of zero or maximum optical density.
Two modes of address may also be distinguished for thermal transfer imaging, namely print head and IR address. In the former, heat is supplied to the donor-receptor assembly via an external print head comprising an array of microresistors, while in the latter the energy is supplied by a radiant source (usually an IR emitter such as a laser) and converted to heat within the donor-receptor assembly by a suitably-placed radiation absorber. Print heads have inherent limitations with respect to resolution (e.g., 400 dpi max.), so that the resolution of the media is less of a problem. Laser scanners can readily achieve greater than 2000 dpi resolution, and so the capabilities of the media become critical. Print head addressable mass transfer media generally comprise a substrate bearing a colorant layer of a waxy resin containing dispersed dyes or pigments, a typical commercially-available example being TLP OHP11, available from Mitsubishi.
IR addressable thermal mass transfer media are well known in the literature see, for example, JP 63-319192, WO 90/12342 and WO 92/06410 and additionally comprise a suitable IR absorbing dye or pigment either within the colorant layer or in a separate layer underneath the colorant layer. It is also possible for the IR absorber to be located in the receptor, as described in our copending PCT Application No. GB 92/01489.
Fluorinated surfactants have also found utility as coating aids in the preparation of transfer media. In addition, such surfactants have been used for other purposes.
U.S. Pat. No. 5,034,371 describes a dye-diffusion transfer donor for printhead address comprising a fluorocarbon additive in addition to dye(s) and binder. The relevant Example teaches about 5 wt % fluorocarbon (FC). Improvements are shown in terms of non-sticking to the receptor and lack of creasing.
JP 61-206694 discloses a mass-transfer donor for printhead address comprising a pigmented layer overcoated with a layer of surfactant, preferably fluorosurfactant. The purpose is to achieve better transfer to poor quality paper.
WO 88/04237 discloses a thermal imaging medium which is laser-addressable, comprising a support sheet having a surface of a material which may be temporarily liquified by heat and upon which is deposited a particulate or porous layer of an image forming substance which is wettable by the material in its liquefied state. Either the image forming substance is itself IR-absorbing, or a separate absorber is present. In exposed areas, the liquefiable material melts, wets the particles of the image forming substance, then resolidifies, thus anchoring the particles to the substrate. Removal of a stripping sheet (either present from the outset or applied subsequent to exposure) then causes selective removal of the particles in the non-exposed areas. The image forming layer may comprise pigment particles with or without binder, but when binder is used the pigment:binder ratio is highxe2x80x94in the range 40:1 to 1:2, preferably 5:1. Surfactants, including fluorosurfactants, may be added, and the examples show the use of Fluorad FC-120 at the level of 2.7 wt % of total solids, which corresponds to a pigment:FC ratio of about 30:1. The stated purpose is to improve coating quality, with no mention of resolution enhancement. This patent application also teaches the addition of submicroscopic particles to the image forming layer in order to improve the abrasion resistance of the final image. Polytetrafluoroethylene is said to be particularly useful, but this embodiment is not demonstrated in the Examples.
It has now been found that the inclusion of relatively large amounts of fluorocarbon compounds in the colorant layer of a mass transfer sheet leads to improved properties, particularly improved resolution.
Therefore according to the present invention there is provided a mass transfer imaging element comprising a substrate bearing a colorant layer containing a pigment which is adapted to be imagewise transferred, in which the colorant layer comprises a fluorocarbon additive in an amount to provide a fluorocarbon additive:pigment weight ratio of at least 1:20.
In accordance with the invention, in both peel-apart and thermal transfer systems, a marked improvement in resolution is seen when the colorant layer additionally contains a fluorocarbon (FC) additive in an amount corresponding to a FC:pigment ratio of at least 1:20, preferably 1:15, more preferably at least 1:10, by weight. In the case of thermal transfer donors, there is also an unexpected improvement in sensitivity. It is believed that the fluorocarbon serves to reduce the cohesive forces within the layer and hence promotes clean xe2x80x9cshearingxe2x80x9d of the layer in the direction perpendicular to its major surface. A further advantage shown by IR-addressed thermal transfer donors of the invention is an improved integrity of transferred dot. During IR address (e.g. by a laser), very high temperatures may be generated within the colorant layer, sufficient to degrade and partially or completely volatilise binder components of the colorant layer. The gas generated as a result may help to propel the pigment particles towards the receptor, and indeed certain prior art patents, e.g., WO 90/12342 and WO 92/06410 advocate the use of thermally-labile, gas-producing compounds to enhance this effect, and so increase the sensitivity. However, a side effect of this is a tendency for the pigment particles to xe2x80x9cscatterxe2x80x9d, producing a less well-defined dot on the receptor. The thermal transfer donors of the present invention do not suffer from this defect, and it is believed that the addition of substantial amounts of thermally-inert fluorocarbon derivatives promotes transfer of the colorant in a molten rather than a vaporised state. Surprisingly, this does not incur a loss of sensitivity; indeed the donor elements of the invention show higher sensitivities than those described in the prior art.
Although fluorocarbons have been incorporated previously in both peel-apart and thermal transfer media, as described above either the quantities involved have been significantly lower than those used in the present invention, or the constructions involved have been of a different type. The improved properties of resolution and sensitivity have no precedent in the prior art. The improvement is significant; U.S. Pat. No. 5,019,549 discloses laser transfer donors similar to the preferred donors of the present invention, but lacking any FC additive. Sensitivities of 0.38 and 0.75 Jcmxe2x88x922. are quoted, which compares unfavourably with the present invention, which can achieve sensitivities of 0.075 Jcmxe2x88x922.
The substrate may be any of the materials commonly used in peel-apart and thermal transfer media, but for reasons of cost, availability, optical clarity, thermal and dimensional stability, polyester is the material of choice. For peel-apart and laser-addressed media the substrate must be transparent. The preferred thickness is different for the different embodiments. Printhead addressed materials require a very thin substrate ( less than 10xcexc), while with peel-apart media there is a trade-off between resolution and handleability. Thinner substrates improve resolution, but at the expense of an increased tendency to crease and wrinkle. A thickness in the range 10-25 microns represents a good compromise, although other ranges may be used. For laser-addressed media, substrate thickness is less critical, and a wide range may be used, e.g., 20 to 200xcexc typically about 100xcexc.
In principle, any pigment (organic or inorganic) may be used, providing it has the desired colour and suitable light-fastness and thermal stability for the purpose intended. Particularly suitable pigments are those currently supplied to the colour proofing industry, as they are available in shades which allow matching of internationally-agreed standards for colour reproduction. Examples of such pigments include 249-0592, 248-0615, 234-0071, 275-0570 (all available from Sun Chemical Co), RV-6853 (Mobay), 1270 (Harshaw) and Raven-760. Other examples are listed in EP 385466 and in the following Examples. The choice of pigment is not limited to those producing the xe2x80x9cconventionalxe2x80x9d colours (yellow, magenta, cyan and black), but extends to other colours, and pigments for special purposes, such as reflective pigments, UV-absorbing pigments, fluorescent pigments and magnetic pigments.
Generally speaking, the smaller the pigment particle size, the better the resolution achievable, but this may be counteracted by other factors such as the quality of the dispersion. A distribution of particle sizes will normally be present, but preferably no particles or agglomerates of particles should be so large as to affect resolution on the micron scale. The quantity of pigment will vary with factors such as layer thickness, the optical density desired, and the optical properties of the pigment itself, but typical values are in the 10-70% by weight of the total involatiles of the colorant layer. For peel-apart elements, the preferred pigment loading is in the range 15 to 30 wt % and for thermal transfer donors it is in the range 35 to 65 wt %.
The colorant layer normally comprises a binder which may be chosen from a wide variety of homopolymers, copolymers and blends of polymers. The main criteria are film-forming ability, optical clarity, solubility in the commonly-used coating solvents (acetone, methyl ethyl ketone (MEK), etc. and compatibility with the pigment. Examples include vinyl polymers such as polyvinylbutyral and polymers and copolymers of vinyl chloride, vinyl acetate, vinyl ethers etc., acrylic polymers such as poly(alkyl acrylates) and poly(alkyl methacrylates), cellulose esters, polyesters, polyamides, polycarbonates, and phenolic resins. Preferred materials include VAGH (a copolymer of vinyl chloride and vinyl acetate (partially hydrolysed) available from Union Carbide) and Resinox 7280 (a phenolic resin available from Monsanto), preferably modified by reaction of a proportion of the phenol groups with a di-isocyanate.
The fluorocarbon additive is present in sufficient quantity to give a FC:pigment ratio of at least 1:20, preferably 1:15 and more preferably at least 1:10. The upper limit depends to a large extent on the structure of the fluorocarbon, the properties of the other ingredients and the end use, but is seldom greater than 1:1. Typical values for photocuring peel-apart media are in the range 1:2 to 1:5. Too little fluorocarbon leads to loss of resolution and/or sensitivity while too much may lead to poor quality coatings lacking structural integrity.
In the case of thermal transfer media, a further factor to be considered is that of overprintability. In order to generate full colour images, it is necessary to transfer several separate monochrome images to a common receptor, and very high levels of fluorocarbon in the transferred colorant can make this difficult. Yet another factor to be considered is the mode of address of the thermal transfer media. As described previously, one function of the fluorocarbon is to help maintain dot integrity during the transfer process, and the amount required to achieve this may vary depending on the conditions under which transfer takes place. For example, address by a relatively high-power laser such as a YAG laser may require higher loadings of the fluorocarbon than when address is by a lower power device such as a laser diode. For these reasons, the preferred loading of fluorocarbon in media designed for thermal transfer imaging extends over a greater range, eg to give FC:pigment ratios in the range 1:3 to 1:15.
A wide variety of fluorocarbon compounds may be used, provided they are substantially involatile under normal coating and drying conditions, and sufficiently miscible with the binder material(s). Thus, highly insoluble fluorocarbon resins such as PTFE, polyvinylidenefluoride, are unsuitable, as are gases and low boiling liquids, such as perfluoroalkanes. With the above exceptions, both polymeric and lower molecular weight materials may be used, although the latter are preferred. Preferably the fluorochemical is selected from compounds comprising a fluoroaliphatic group attached to a polar group or moiety and fluoropolymers having a molecular weight of at least 750 and comprising a non-fluorinated polymeric backbone having a plurality of pendant fluoroaliphatic groups, which aliphatic groups comprise the higher of
(a) a minimum of three Cxe2x80x94F bonds, or
(b) in which 25% of the Cxe2x80x94H bonds have been replaced by Cxe2x80x94F bonds such that the fluorochemical comprises at least 15% by weight of fluorine.
The fluoroaliphatic group is generally a fluorinated, preferably saturated, monovalent, aliphatic group of at least two carbon atoms. The chain may be straight, branched, or, if sufficiently large, cyclic, and may be interrupted by oxygen atoms or nitrogen atoms bonded only to carbon atoms. A fully fluorinated group is preferred, but hydrogen or chlorine atoms may be present as substituents in the fluorinated aliphatic group; generally not more than one atom of either is present in the group for every two carbon atoms. Preferably the group contains a terminal perfluoromethyl group. Preferably, the fluorinated aliphatic group contains no more than 20 carbon atoms.
Non-polymeric fluorochemical additives generally comprise lower molecular weight fluorinated compounds and contain at least 15% (preferably 20%) by weight of fluorine, and are substantially involatile under atmospheric pressure at temperatures up to 50xc2x0 C., preferably up to 100xc2x0 C., most preferably up to 150xc2x0 C. Such materials commonly comprise a fluorinated aliphatic group attached to a polar group or moiety such as carboxylic acid (and salts thereof), phosphoric acid (and salts thereof), sulphonic acid (and salts thereof), acid halide, sulphonyl halide, ether, ester, amide, sulphonamide, polyether, urethane, carbonate, urea, carbamate etc.
Suitable polymeric fluorochemical additives include a wide range of polymeric and oligomeric materials generally having a molecular weight of at least 750, preferably at least 1000, which materials comprise a polymeric or oligomeric backbone having a plurality of pendant fluoroaliphatic groups. The polymeric backbone may comprise any suitable homopolymer or co-polymer known to the art including, for example, acrylates, urethanes, polyesters and polycarbodiimides. Co-polymers of fluorinated and non-fluorinated monomers are also useful. Generally the fluoropolymer has a minimum fluorine content of 15%, and preferably 20% by weight.
Generally where the backbone comprises hetero-atoms (e.g., oxygen, nitrogen, sulphur etc.) in addition to carbon atoms, then fluorine may be present as a backbone substituent. Where the backbone comprises solely carbon atoms, then the fluorine substituents are usually confined to the pendant fluoroaliphatic groups, the backbone remaining fluorine free. Thus, fluorinated polyethers, polyesters, polyurethanes or other polymers formed by ring opening or condensation polymerisation are included, but the highly insoluble polymers and copolymers of tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, vinyl fluoride, vinylidene fluoride etc. are excluded.
The fluoropolymer preferably comprises an acrylate homopolymer or co-polymer backbone supporting a number of fluoroaliphatic groups. The term acrylate is used in the generic sense and is intended to include not only derivatives of acrylic acid but also methacrylic acid and other modified acrylic acids.
Each acrylate monomer may possess one or more fluoroaliphatic groups in which the higher of (a) a minimum of three Cxe2x80x94F bonds are present or (b) 25% of the Cxe2x80x94H bonds have been replaced by Cxe2x80x94F bonds. Each acrylate monomer incorporates at least one polymerisable vinyl group.
Suitable fluorochemicals are disclosed on page 3 lines 18 to 39 of EP 0433031. Compounds A-1 to A45 and B1 to B3 listed in U.S. Pat. No. 5,034,371 cols 38 to 40 are also useful. Other suitable fluorocarbons are disclosed in U.S. Pat. Nos. 2,567,011, 2,732,398, 2,803,615, 2,803,656, 3,078,245, 3,544,537, 3,574,791, 3,787,351, 4,015,612 4,049,861, 4,167,617 and 4,340,749. Fluorocarbons bearing polymerisable unsaturated groups are particularly suitable for the peel-apart systems because they can participate in the photocuring reaction.
In addition to the above ingredients, peel-apart elements of the invention comprise a photocuring system, which normally consists of one or more polymerisable monomers, a photoinitiator and optionally a sensitiser. Any of the commonly-used unsaturated monomers may be used, but preferably at least a proportion of the monomers are at least bifunctional, so that a crosslinked network is produced on curing. Suitable monomers are disclosed for example, in EP 0385466A. Preferred monomers include trimethylolpropane trimethacrylate, ethyleneglycol dimethacrylate, tetraethyleneglycol dimethacrylate and tripropyleneglycol dimethacrylate. The monomers typically constitute 30 to 50 wt % of the involatiles in the colorant layer, but this may vary depending on the nature of the other ingredients.
A wide variety of photoinitiators may be used, including those disclosed on pages 5 to 6 of EP 385466. Preferred initiators include trichloromethyltriazine derivatives and onium salts such as iodonium and sulphonium salts. If necessary, a sensitiser may be included. For colour proofing purposes, it is highly desirable that the initiator and sensitiser should not absorb significantly in the visible range of the spectrum to avoid contaminating the final coloured image. Thus, initiator systems sensitive to the UV are most commonly used, although sensitisation to the IR is also possible, e.g., using the initiator-sensitiser combinations disclosed in EP 444786.
In addition to the basic ingredients of binder, pigment and fluorocarbon, the colorant layer of thermal transfer donors in accordance with the invention may include other ingredients such as plasticisers and IR absorbers. A plasticiser may be added to lower the softening temperature of the final coating, and normally comprises a high-boiling liquid or low-melting solid. The polyfunctional monomers listed above have proved useful in the context, e.g., at a loading of 25% of the total solids, but with a suitable choice and quantity of fluorocarbon, addition of plasticiser is unnecessary. If the thermal transfer donor is to be imaged by IR radiation, then a suitable absorber may be incorporated in the colorant layer, or in an underlayer. Alternatively, the absorber may be present in a layer coated on the receptor to which the image is to be transferred, as described in our copending PCT Application No. GB 92/01489. Essentially any dye or pigment providing a suitable IR absorption may be used, including those disclosed in Japanese Patent Applications Nos. 51-88016 and 63-319192. A layer of vapour-deposited metal or metal oxide, as described in WO 92/06410, may be used. Dyes or pigments which have minimal absorption in the visible region, or which bleach during imaging, are preferred, particularly if they are to be incorporated in the colorant layer itself. IR dyes with minimal visible absorption include the croconium dyes described in British Patent Application No. 9209047.1, the phthalocyanines described in EP 157568, and the aromatic diamine dication-type dyes described on pages 6 to 8 of WO 90/12342, of which Cyasorb IR 165 (American Cyanamid) is a good example. Dyes that require long alkyl chain substituents for solubility may interact unfavourably with the fluorocarbon additive, and are not preferred.
The solutions used to coat the colorant layers may be conveniently prepared by roll-milling the pigment and binder in accordance with known techniques to give xe2x80x9cpigment chipsxe2x80x9d, adding solvent (acetone, MEK etc) to produce xe2x80x9cmillbasexe2x80x9d, then adding the remaining ingredients and further solvent as required. Different pigment chips can be mixed in order to obtain the desired L* a* b* values for SWOP colour matching.
Alternatively, two pigment chip millbases can be mixed in the desired ratio to obtain the desired L* a* b* values. It is highly preferred to add the fluorocarbon to a predispersion of the pigment and binder, otherwise much of its beneficial effect may be lost.
The layers may be coated by any of the conventional means, along with whichever other layers are required by the particular construction.
The invention is applicable to peel-apart constructions known in the art and is particularly useful in the colour sheets for full colour proofing disclosed in our British Patent Application of even date. That application discloses a colour sheet suitable for use in colour proofing comprising a substrate bearing a layer of pigmented photopolymerisable material overcoated with a barrier layer and an outer layer of an adhesive.
The application also discloses a method of preparing a full colour proof which comprises laminating a colour sheet as defined above to a support base, exposing the sheet through its substrate, peeling the substrate from the sheet to remove unexposed regions of the pigmented photopolymerisable material, repeating the lamination, exposure and peeling steps with three additional colour sheets to build up a full colour proof comprising cyan, magenta, yellow and black layers.
The advantages of the system over prior art are that whilst it allows for the least polyester waste and a simple customer assembly in a minimum number of steps, the barrier layer which is normally poly(vinyl alcohol) also allows for solvent coating of adhesives during manufacture. Prior art methods for construction of a surprint negative acting dry-developed proof either involve more plastic support wastage or an additional number of steps (which lowers customer productivity) or both.
Imaging of the thermal mass transfer donor elements of the invention is carried out by assembling the donor in intimate contact with a suitable receptor (usually under pressure) and supplying an imagewise pattern of thermal energy via a printhead or IR radiation as appropriate, such that areas of colorant layer are transferred to the receptor in accordance with the image information. Peeling of the donor from the receptor reveals matched positive and negative images on the donor and receptor respectively. The process may be repeated using donors of different colours (or a single donor coated with patches of different colours, as described in U.S. Pat. No. 4,503,095, may be used), so that a multi-colour image is built up on the receptor. If desired, this can be retransferred to another substrate, e.g., plain paper. Alternatively, the positive images remaining on the donor sheets may be assembled into a final image, e.g., by overlaying in register or transfer in register to a common substrate.
Any of the known methods of IR address may be used, including direct address by a laser pulsed in accordance with digitised image information; flood exposure through a suitable mask from a source such as a xenon arc, tungsten bulb etc, as described in Research Disclosure No. 142223; and exposure through a mask by a scanned continuous source, as described in UK Patent Application No. 9217095.0. Preferred lasers for use with the invention include diode lasers (e.g. GaAs lasers), Nd-YAG lasers and Nd-YLF lasers.
The invention will now be illustrated by the following Examples.
In the Examples the following abbreviations are used to identify the fluorochemicals.
F1 N-butylperfluorooctanesulphonamido ethyl acrylate.
F2 a fluorochemical acrylate oligomer disclosed in U.S. Pat. No. 3,787,351, Example 1.
F3 perfluorooctanoic acid.
F4 perfluorooctanesulphonamido ethyl alcohol.
F5 1,1-dihydro-2,5-bis(trifluoromethyl) 3, 6, dioxaperfluorodecyl methacrylate.
F6 N-methyl perfluorooctanesulphonamide
F7 N-methyl, N-glycidyl perfluorooctanesulphonamide.
F8 N-Ethyl, N-vinyloxyethyl perfluorooctanesulphonamide.
F9 Methylene bis(trifluoromethylsulphone).
F10 N-Ethyl, N-omega-methoxy poly(methyleneoxy) ethyl perfluorooctanesulphonamide.